Process for the pad-dyeing and printing of textile material of polyacrylonitrile which contains sulfonic acid groups

ABSTRACT

Process for the dyeing of textile material of polyacrylonitrile which contains sulfonic acid groups, which comprises using as carriers compounds of the general formula   in which R1, R2 and R3 each represent a hydrogen, chlorine or bromine atom, an alkyl or alkoxy group of 1 to 4 carbon atoms or a nitro group, Ar represents a benzene or naphthalene ring, R4 represents a hydroxy-alkyl group of 1 to 4 carbon atoms, and R5 represents a hydrogen atom, an alkyl or hydroxy-alkyl group of 1 to 4 carbon atoms, a cyanoethyl group, an alkenyl group of 2 to 4 carbon atoms, a benzyl or cyclohexyl group. By using these compounds as carriers deep shades with an excellent levelness can be obtained and due to their high boiling point the danger of forming so-called carrier-spots on the goods is diminished.

United States Patent 1w: Ong et al.

I PROCESS FOR THE PAD-DYEING AND PRINTING OF TEXTILE MATERIAL OFPOLYACRYLONITRILE WHICH CONTAINS SULFONIC ACID GROUPS 175] Inventors:Sienling Ong, Lorsbuch, Taunus.

German); Helmut Dier), Paris. France; Hans-.Iiirgen Weyer.Bergen-Enkheim. German [73] Assignee: Hoechst Aktiengesellschaft.

Frankfurt am Main. Germany [22] Filed: June 27, I974 [21] Appl. No:483.565

FOREIGN PATENTS OR APPLICATIONS 23.130 11/1967 Japan 8/167 1 1 Nov. 11,1975 Primary Emnn'uer-Lewis T. Jacobs .-illrum' Agent. or Firm-Curtis.Morris & Safford [57] ABSTRACT Process for the dyeing of textilematerial of polyacrylonitrile which contains sulfonic acid groups. whichcomprises using as carriers compounds of the general formula in whichR,. R and R each represent a hydrogen. chlorine or bromine atom, analkyl or alkoxy group of l to 4 carbon atoms or a nitro group. Arrepresents a benzene or naphthalene ring. R represents a hydroxyalkylgroup of 1 to 4 carbon atoms. and R represents a hydrogen atom. an alkylor hydroxyalkvl group of 1 to 4 carbon atoms. a cyanoethyl group. analkenyl group of 2 to 4 carbon atoms. a benzyl or cyclohexyl group. Byusing these compounds as carriers deep shades with an excellentlevelness can be obtained and due to their high boiling point the dangerof forming so-called carrier-spots on the goods is diminished.

2 Claims. N0 Drawings 1 PROCESS FOR THE PAD-DYEING AND PRINTING OFTEXTILE MATERIAL OF POLYACRYIDNITRILE WHICH CONTAINS SULFONIC ACIDGROUPS The present invention relates to a process for the pad-dyeing andprinting of textile material of polyacrylonitrile which containssulfonic acid groups.

It is known that in the dyeing of synthetic fibrous materials so-calledcarriers must be used in order to obtain a sufficient color intensity.These carriers act as swelling agent on the fiber and facilitate therebythe penetration of the dyestuff molecule into the fiber.

Now, we have found a process for the dyeing of textile material ofpolyacrylonitrile which contains sulfonic acid groups, which comprisesusing as carriers compounds of the general formula in which R R, and Reach represent a hydrogen, chlorine or bromine atom, an alkyl or alkoxygroup of l to 4 carbon atoms or a nitro group, Ar represents a benzeneor naphthalene ring, R, represents a hydroxy-alkyl radical of l to 4carbon atoms and R, represents a hydrogen atom, an alkyl orhydroxy-alkyl group of i to 4 carbon atoms, a cyanoethyl group, analkenyl group of 2 to 4 carbon atoms, a benzyl group or a cyclohexylSuitable aryl-sulfonamides of the above-specified formula are, forexample, the following compounds: N- hydroxyethyl-benzenesulfonamide,N-hydroxypropylbenzene-sulfonamide,N-hydroxyethyl-N-methyl-benzenesulfonamide,N-hydroxyethyl-N-allyl-benzenesul fonamide,N-hydroxypropyl-N-cyanoethylbenzenesub fonamide,N-hydroxyethyl-N-methyl-p-chlorobenzenesulfonamide,N-hydroxyethyl-N-ethyl-ochlorobenzenesulfonarnide,N-hydroxyethyl-N-methyltoluenesulfonamide, N-hydroxyethyl-N-methyl-2,4-dichloro-S-methyI-benzenesulfonamide,N-bis-hydroxyethyl-benzenesulfonamide,N-hydroxyethyl-N-methyl-2,S-dichlorobenzenesulfonamide, toluene-bis-(N-hydroxyethyl-N-methyl-sulfonamide), N-hydroxyethyl-N-n-butyl-4-chlorobenzenesulfonamide,N-S-hydroxypropyl-N-rnethyl-4-chlorobenzenesulfonamide, N-hydroxyethyl-N-cyclohexyl-4-chlorobenzenesulfonamide,N-2-hydroxypropyl-N-methyl-4-chlorobenzenesulfonamide,N-hydroxyethyl-N-methyl-B-naphthalene-sulfonamide,N-hydroxyethyl-N-methyl-mnitrobenzenesulfonamide,N-hydroxyethyl-N-ethyl-pmethoxybenzenesulfonamide, N-2-hydroxybutyl-N-methyl-benzenesulfonamide, N-Z-hydroxyethyl-N-B-cyanoethyl-4-chlorobenzenesulfonamide, naphthalenel ,5 -bis(N-hydroxyethyl )-N-methyl-sulfonamide).

N-Methyl-N-hydroxyethyl-p-chlorobenzenesulfonamide andN-ethyl-N-hydroxyethyl-p-chlorobenzenesulfonamide as well as mixtures ofthese two compounds have a particularly good carrier action.

The arylsulfonamides of the above-specified formula are preparedaccording to known methods, for example by reacting the correspondingaromatic sulfochloride in an aqueous medium and in the presence ofsodium hydroxide solution with a mono-substituted amine. The resultingN-mono-substituted aryl-sulfonamide is subsequently further reacted withalkylating agents, for example dimethyl sulfate, diethyl sulfate ordibutyl sulfate. It is also possible to react the aromaticsulfochlorides directly with the correspondingly substituted secondaryamines.

The aryl-sulfonamides are added to the printing pastes or paddingliquors during their preparation. The quantity required depends on thetextile material to be dyed and the desired color intensity. It can beeasily determined by preliminary tests. In general, 10 g ofaryl-sulfonamide per kilogram of printing paste or padding liquor arenecessary. The aryl-sulfonamides are advantageously used together withnon-ionic emulsifiers. The quantity of emulsifier is suitably 2 to 20 byweight, referred to the aryl-sulfonamide.

The padding liquors or printing pastes are applied onto the goodsaccording to the conventional methods. The goods are then fixed, forexample by steaming them in wet state at temperatures in the range offrom 102 to C at normal pressure. The steaming times depend on thetemperature of the steam and on the nature of the printed or pad-dyedgoods and are in general between 2 and 40 minutes, preferably between 3and 20 minutes. The substrates of polyacrylonitrile containing 'sulfonicacid groups used in the.process of the invention are described, forexample in German Patent Specification l,066,022. As dyestuffs, theremay be used the basic dyestuffs usually employed in the dyeing ofpolyacrylonitrile, for example those described in the Colour IndexVolume V, page 5073 5086, 3rd Edition (1971). i

With the above-described process, shaped structures such as filaments,fibers, fabrics, knit-fabrics, carpets, films and foils ofpolyacrylonitrile which contains sulfonic acid groups can be dyed withbasic dyestuffs deep shades that have outstanding levelness. Over thebis-B- cyanoethyl-formamide hitherto used as carrier for such textilefibers, the carriers used in this process have the advantage of having ahigher boiling point, so that during fixation of the goods the steamingchamber is not saturated with carrier vapours. When low-boiling carriersare used, the carrier vapour condenses on cold parts in the steamingchamber and in its exhaust duct under formation of droplets which canfall down on the goods and cause there the feared carrier spots.Furthermore, the arylsulfonamides used according to the invention areless toxic. These advantages also hold over the known carriersdichlorophenoxyethanol and 4-chlorophenoxyethanol. In comparison withthese carriers, the aryl-sulfonamides used according to the inventionhave the advantage of having an essentially lower hardening effect onthe fibers which is due to the influence of the carrier. in addition,the aryl-sulfonamide have a certain solubility in water so that they canbe easily washed out and therewith have no deteriorating influence onthe fastness to light of the prints or dyeings.

The following Examples illustrate the invention.

EXAMPLE 1 Carpet goods of polyacrylonitrile which contained sulfonicacid groups was printed with a printing paste which contained thefollowing components:

20 g of the dyestufi' Basic Red No. l8

(CI. Number H085).

After printing, the goods were steamed in undried state for 8 minutes ina steamer and subsequently washed thoroughly. Bright red printedpatterns on a white ground having very good properties of fastness wereobtained.

EXAMPLE 2 Carpet goods of polyacrylonitrile containing sulfonic acidgroups were printed with a printing paste which had the followingcomposition:

of the dyestufl' Basic Blue No. 3 (Cl. Number 51004), of aqueous aceticacid of 80% strength, of hot water, of a 4 aqueous solution of a locustbean flour derivative, of a mixture of 85 parts by weight of N-ethyl-N-hydroxy-ethyLp-chlorobenzenesulfonamide and l5 parts by weight of afatty acid oxethylate. and 575 g of water.

I kg.

8 Est The printed goods were subsequently steamed for 15 minutes in asteamer at 102 C and washed as usual. Fast brilliant blue prints wereobtained on the carpet goods.

EXAMPLE 3 A fabric of polyacrylonitrile containing sulfonic acid groupswas padded with a dyeing liquor which had the following composition:

10 g of the dyestuff Basic Red No l8 (C.l. Number H085),

10 g of the dyes-tuft Basic Blue No. 3

(Cl. Number 5l004).

of acetic acid having k strength.

of a 4 aqueous solution of a locust bean flour derivative,

'of a mixture of parts by weight ofN-2-hydroxyethyl-N-ficyanoethyl-dchlorobenzenesulfonamide and 10 partsby weight of a non-ionic emulsifier. and

835 ml of water,

I kg.

in which R R and R each is hydrogen, chlorine, bromine, alkyl or alkoxyof l to 4 carbon atoms or nitro, Ar is a phenyl or naphthalene ring, Ris hydroxy-alkyl of l to 4 carbon atoms, and R is hydrogen, alkyl orhydroxy-alkyl of l to 4 carbon atoms, cyanoethyl, alkeny] of 2 to 4carbon atoms, benzyl or cyclohexyl.

2. A process as claimed in claim 1, wherein the compound used as carrieris N-methyl-N-hydroxyethyl-pchlorobenzenesulfonamide orN-ethyl-N-hydroxyethylp-chlorobenzenesulfonamide or a mixture thereof.

i i i l I.

1. PROCESS FOR THE DYEING OF TEXTILE MATERIAL OF POLYACRYLONITRILE WHICHCONTAINS SULFONIC ACID GROUPS, WHICH COMPRISES USING AS CARRIER ACOMPOUND OF THE FORMULA
 2. A process as claimed in claim 1, wherein thecompound used as carrier isN-methyl-N-hydroxyethyl-p-chlorobenzenesulfonamide orN-ethyl-N-hydroxyethyl-p-chlorobenzenesulfonamide or a mixture thereof.